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Immobilization of mercury and zinc in an alkali-activated slag matrix.

The behavior of heavy metals mercury and zinc immobilized in an alkali-activated slag (AAS) matrix has been evaluated using physical property tests, pore structure analysis and XRD, TG-DTG, FTIR and TCLP analysis. Low concentrations (0.5%) of mercury and zinc ions had only a slight affect on compressive strength, pore structure and hydration of AAS matrixes. The addition of 2% Hg ions to the AAS matrix resulted in a reduction in early compressive strength but no negative effects were noticed after 28 days of hydration. Meanwhile, 2% Hg ions can be effectively immobilized in the AAS matrix with the leachate meeting the USEPA TCLP mercury limit. For a 2% Zn-doped AAS matrix, the hydration of the AAS paste was greatly retarded and the zinc concentration in the leachate from this matrix was higher than 5mg/l even at 28 days. Based on these results, we conclude that the physical encapsulation and chemical fixation mechanisms were likely to be responsible for the immobilization of Hg ions in the AAS matrix while only chemical fixation mechanisms were responsible for the immobilization of Zn ions in the AAS matrix.

Compressive Strength↗

Stabilization/solidification of waste ferrous sulphate from titanium dioxide production by fluidized bed combustion product.

A treatment procedure to allow the disposal of waste ferrous sulphate was developed. This waste contains sulphuric acid and originates from titanium dioxide production. The process is based on simultaneous neutralization and stabilization/solidification (S/S) of the waste by means of fluidized bed combustion product (FBC-P). The prepared stabilized waste specimens have a solid matrix and their batch leachates display practically neutral pH and also satisfactory conductivity values. The leachate composition is notable in its absence of toxic metals and even iron.

Coloring Agents↗

Perpetual landfilling through aeration of the waste mass; lessons from test cells in Georgia (USA).

Municipal solid waste (MSW) landfills worldwide are experiencing the consequences of conventional landfilling techniques, whereby anaerobic conditions are created within the landfilled waste. Under anaerobic conditions within a landfill site slow stabilization of the waste mass occurs, producing methane, (an explosive 'green house' gas) and leachate (which can pollute groundwater) over long periods of time. As a potential solution, it was demonstrated that the aerobic degradation of MSW within a landfill can significantly increase the rate of waste decomposition and settlement, decrease the methane production and leachate leaving the system, and potentially increase the operational life of the site. Readily integrated into the existing landfill infrastructure, this approach can safely and cost-effectively convert a MSW landfill from anaerobic to aerobic degradation processes, thereby effectively composting much of the organic portions (one of the potentially polluting elements in a conventional landfill site) of the waste. This paper summarizes the successful results of two separate aerobic landfill projects located in Georgia (USA) and discusses the potential economic and environmental impacts to worldwide solid waste management practices.

Air Movements↗

A study of Cr(VI) in ashes from fluidized bed combustion of municipal solid waste: leaching, secondary reactions and the applicability of some speciation methods.

The use of the fluidized bed technique for the combustion of municipal solid waste is a rather new concept. This type of combustor produces ash residues with somewhat different properties than the residues generated from the traditional mass burn techniques. Therefore, chemical characterization and the investigation of toxic metals behavior during ash water reactions are necessary for the safe disposal of these residues. In the present work, the total elemental composition, mineralogy and leaching behavior of ashes from the combustion of municipal solid waste in a fluidized bed combustion boiler have been investigated. The cyclone ash and, in particular, the filter ash contained considerable amounts of soluble substances, thus giving leachates with high levels of Cl-, Na+, K+, Ca2 + and Al(IIl). On the other hand, the two ash fractions taken in the boiler, the bottom and hopper ashes, were much more stable with respect to the release of salts and heavy metals. Since Cr(VI) is mobile and toxic its release from combustion residues can pose environmental problem. Even though the total Cr contents were similar in all ashes studied, the bottom ash gave about a thousand times higher levels of Cr(VI) in test leachates than the hopper, cyclone and filter ashes. However, it was found that the leached amount of Cr(VI) from the bottom ash decreased significantly when bottom ash was mixed with the hopper ash. The most probable cause for this decrease is the coupled oxidation of Al(0) to Al(III) and reduction of dissolved Cr(VI) to Cr(III). This finding that the mixing of two ash streams from the same boiler could result in the immobilization of Cr may point at a simple stabilization method. Selective extraction of water soluble, exchangeable and sparingly soluble forms of Cr(VI) was also investigated. Extraction methods were evaluated for their suitability for ash matrixes. It was found that interferences due to the presence of reducing substances in some ash materials may occur.

Aluminum↗

A comparison of small-scale, pilot-scale and large-scale tests for predicting leaching behaviour of landfilled wastes.

Landfills generate emissions over long periods, often longer than a lifetime. The longest lasting emission is leachate. In order to estimate the future requirements for leachate treatment, different kinds of leaching tests may be applied. In this paper, shaking leaching tests (SLT), landfill-simulator leaching tests and a field-cell leaching test performed with ash, municipal solid waste (MSW) and MSW+ash are evaluated. The tests are compared and the factors influencing leaching are identified and discussed. The factors are: liquid to solid (L/S) ratio, water withdrawal, recirculation rate, presence or absence of biological processes, size of particles, duration of experiment, temperature and pre-treatment of the waste. The presence of biological processes has the greatest impact on leaching and is the main reason why SLT is less useful for long-term predictions. The landfill simulator tests were found to be useful for several different kinds of predictions. However, they are not reliable for predicting the L/S required for reaching a certain concentration. The possibilities for reliable long-term predictions would be facilitated by a better knowledge of the influence of various factors on leaching. Such an increased knowledge would make it possible to enhance waste stabilisation in leaching tests as well as in full-scale landfills.

Forecasting↗

Assessment and analysis of industrial liquid waste and sludge disposal at unlined landfill sites in arid climate.

Municipal solid waste disposal sites in arid countries such as Kuwait receive various types of waste materials like sewage sludge, chemical waste and other debris. Large amounts of leachate are expected to be generated due to the improper disposal of industrial wastewater, sewage sludge and chemical wastes with municipal solid waste at landfill sites even though the rainwater is scarce. Almost 95% of all solid waste generated in Kuwait during the last 10 years was dumped in five unlined landfills. The sites accepting liquid waste consist of old sand quarries that do not follow any specific engineering guidelines. With the current practice, contamination of the ground water table is possible due to the close location of the water table beneath the bottom of the waste disposal sites. This study determined the percentage of industrial liquid waste and sludge of the total waste dumped at the landfill sites, analyzed the chemical characteristics of liquid waste stream and contaminated water at disposal sites, and finally evaluated the possible risk posed by the continuous dumping of such wastes at the unlined landfills. Statistical analysis has been performed on the disposal and characterization of industrial wastewater and sludge at five active landfill sites. The chemical analysis shows that all the industrial wastes and sludge have high concentrations of COD, suspended solids, and heavy metals. Results show that from 1993 to 2000, 5.14+/-1.13 million t of total wastes were disposed per year in all active landfill sites in Kuwait. The share of industrial liquid and sludge waste was 1.85+/-0.19 million t representing 37.22+/-6.85% of total waste disposed in all landfill sites. Such wastes contribute to landfill leachate which pollutes groundwater and may enter the food chain causing adverse health effects. Lined evaporation ponds are suggested as an economical and safe solution for industrial wastewater and sludge disposal in the arid climate of Kuwait.

Animals↗

Hydrological performance of MSW incineration residues and MSW co-disposed with sludge in full-scale cells.

Water flows were analysed for the filling phase and the first 4 years after closure of two types of full-scale landfill cells: 'special cells' containing mostly fly ash from municipal solid waste (MSW) incineration disposed with other special/hazardous waste, and 'biocells' (biological cells) containing co-disposed MSW and food industry sludge. The landfill cells were constructed about -1.5 m above sea level (masl) at Lomma Bay, southern Sweden. The hydrological effects of water intrusion into the special cells from surroundings and sludge moisture within the biocells were studied. HELP modelling of hydrological processes predicted delay in peaks of leachate generation from uncovered special cells following rain, which was not confirmed. Faster leachate production as a response to rainfall from special cells than from biocells was observed. It was inferred that special waste has more intensive channelling, lower water absorption and higher hydraulic conductivity than mixtures of sludge/MSW. To avoid convergence problems in modelling uncovered special cells, the use of a 5 cm deep top layer with saturated hydraulic conductivity 1.7 x 10(-3) cm s(-1), porosity 0.437, and field capacity 0.105, is suggested.

Bioreactors↗

A review of aqueous-phase VOC transport in modern landfill liners.

Leachates from municipal solid waste (MSW) and hazardous waste landfills contain a wide range of volatile organic compounds (VOCs) in addition to inorganic compounds. VOCs have been shown to migrate and contaminate the surrounding environment and impair the use of groundwater. Therefore, the effectiveness of modern landfill liner systems to minimize migration of VOCs is of concern. Most modern landfills employ a composite liner consisting of a geomembrane overlying a compacted clay liner or a geosynthetic clay liner. The geomembrane is often believed to be the primary barrier to contaminant transport. However, for VOCs, the clay component usually controls the rate of transport since VOCs are shown to diffuse through geomembrane at appreciable rates. Additionally, analyses have shown that transport of volatile organic compounds (VOCs) generally is more critical than transport of inorganic compounds (e.g., toxic heavy metals), even though VOCs are often found at lower concentrations in leachates. Therefore, the effectiveness of modern landfill liner systems to minimize migration of VOCs and transport of VOCs through clay liners and modeling of transport through composite liners merit scrutiny. This paper presents a review of recent research by the author and others on these topics. A systematic and comprehensive approach to determine mass transport parameters for transport of VOCs in liquid phase through compacted clay liners, geosynthetic clay liners (GCLs), and geomembranes has enabled to develop realistic models to predict mass flux of VOCs through modern composite liners and provide a quantitative basis to evaluate potential for transport of dissolved VOCs and the equivalency of different composite liners.

Aluminum Silicates↗

Changes in constituent equilibrium leaching and pore water characteristics of a Portland cement mortar as a result of carbonation.

Two equilibrium-based characterization protocols were applied to ground samples of a cement-based material containing metal oxide powders in both noncarbonated and carbonated states. The effects of carbonation were shown through comparison of (i) material buffering capacity, (ii) constituent equilibrium as a function of leachate pH, and (iii) constituent solubility and release as a function of liquid-to-solid (LS) ratio. As expected, the material alkalinity was significantly neutralized during carbonation. In addition, carbonation of the cement material led to the formation of calcium carbonate and a corresponding increase in arsenic release across the entire pH range. The solubility as a function of pH for lead and copper was lower in the alkaline pH range (pH>9) for carbonated samples compared with the parent material. When solubility and release as a function of LS ratio was compared, carbonation was observed to decrease calcium solubility, sodium and potassium release, and ionic strength. In response to carbonate solid formation, chloride and sulfate release as a function of LS ratio was observed to increase. Trends in constituent concentration as a function of LS ratio were extrapolated to estimate pore water composition at a 0.06 mL/g LS ratio. Significant differences were observed upon comparison of estimated pore water composition to leachate concentrations extracted at LS ratio of 5 mL/g. These differences show that practical laboratory extractions cannot be assumed directly representative of pore water concentrations.

Carbon↗

Two-phase anaerobic digestion of spent tea leaves for biogas and manure generation.

Anaerobic digestion of spent tea leaves from an instant tea manufacturing factory was studied in a two-phase digester. The hydrolysis and acidification phase resulted in the formation of high organic strength liquid called leachate, with a chemical oxygen demand (COD) of 12,880 mg/l, within the retention time of 10 days. The leachate was tested in a batch methanaogensis reactor for biogas production. An average biogas yield of 0.48 m3/kg of COD destroyed was obtained with an average COD reduction of 93%. The biogas was analyzed for 73% methane content.

Anaerobiosis↗

Detection of genotoxic effects of heavy metal contaminated soils with plant bioassays.

Aim of the present study was the development of a bioassay which enables the detection of genotoxic effects of heavy metal contaminated soils. In the first part of the present study, the data base on metal effects in plant bioassays was extended. Four metal salts, namely Cr(VI)O3, Cr(III)Cl3, Ni(II)Cl2 and Sb(III)Cl3 were tested comparatively in MN tests with pollen tetrad cells of Tradescantia clone #4430 and in meristematic root tip cells of Vicia faba. With Cr6+ and Ni2+, clear-cut dose-effects were observed in a range between 0.75 and 10.0 mM, whereas this was not the case with Cr3+ (range tested 1.25-10 mM) and Sb3+ (range 0.30-5.25 mM). In Vicia, negative results were obtained with the four metal salts under all conditions of test. To compare the mutagenic potencies of the metals, the increases of the regression curves (k-values) were calculated, they indicate the number of MN induced per mM in 100 tetrad cells. The corresponding values for Cr6+ and Ni2+ are 0.87 and 1.05, respectively. It appears that the Tradescantia system is in particular sensitive towards those metal species which cause DNA damage in animals and man such as Cr6+, Cd2+, Ni2+, and Zn2+, whereas no clear positive results were obtained with less harmful metal ions such as Cu2+, Cr3+ or Sb3+. In the second part of the study, the mutagenic effects of four metal contaminated soils and two types of standardized leachates (pH 4.0 and pH 7.0) of these soils were tested in Tradescantia and in Vicia. In addition, chemical analyses were carried out to determine the metal concentrations in the soils and in the extracts. Two of the samples contained highly elevated levels of a number of metals (Zn, Pb, Cu, Cd, Sb, As), one soil came from the Central Austrian Alps and contained high As levels only. Direct exposure of the Tradescantia plants in the soils resulted in a drastic increase of the MN frequencies over the background. The lowest effect was seen with the Slovakian soil which contained in particular Sb and As (4.5-fold increase over the background), with the other soils, the induced frequencies were 11-15-fold over the control values. On the contrary, negative results were obtained upon exposure of Tradescantia cuttings in the leachates and upon implantation of germinated Vicia beans in the soils. The results of the present study indicate that Trad-MN assays with direct exposure of intact plants is an appropriate method which enables to detect genotoxic effects of metal contaminated soils in situ. This simple and fast biomonitoring assays might be a valuable supplement to analytical analyses of contaminated soils.

Antimony↗

Formation of artifact methylmercury during extraction from a sediment reference material.

We examined monomethylmercury (MMHg) in sediment reference material IAEA-405 and sediments from Long Island Sound. MMHg was extracted by both aqueous distillation and leaching with dilute solutions of nitric acid. MMHg was formed from both ambient and added inorganic mercury in extracts of IAEA-405 by either technique. Artifact MMHg in IAEA-405 was related linearly with ambient reactive mercury (HgR) in leachates having > 1.2 M acid, but little or no artifact was measured in less acidic extracts. Addition of potassium chloride enhanced extraction of HgR from LAEA-405 but had no effect on artifact MMHg for each leachate molarity tested. Mercury methylation occurred in solution and was a function of both the availability of HgR and a methylation potential, being limited by HgR in less acidic solutions (0.5-1.2 M) and by the methylation potential in more acidic ones (> 1.2 M). Formation of artifact MMHg in Long Island Sound sediments was inconclusive, but additions of inorganic mercury demonstrated that a potential exists. A potential for abiotic mercury methylation seems always present in sediment, and the availability of HgR appears to control MMHg production under environmental conditions. Abiotic methylation of mercury may occur in environs where the reactivity of inorganic mercury is enhanced, such as river-seawater mixing zones.

Artifacts↗

Modeling of solid/liquid/gas mass transfer for environmental evaluation of cement-based solidified waste.

A physicochemical and transport model has been developed for the long term prediction of environmental leaching behavior of porous materials containing inorganic waste solidified with hydraulic binders and placed in a reuse scenario. The reuse scenario considered in the paper is a storage tank open to the atmosphere including material leaching with water and carbonation through the leachate contact with air. The model includes three levels: (i) the physicochemical pollution source term (chemical equilibria in the pore water and diffusion in the porous system); (ii) chemical equilibria and mass transfer in the tank; and (iii) gas/liquid transfer of carbon dioxide. The model was applied to the case of a material obtained through solidification of Air Pollution Control (APC) residues from Municipal Solid Waste Incinerator (MSWI). The simulation results are in good agreement with two scale experimental data: laboratory and field tests. Experimental data and simulations show the main trends for release of elements contained in the material: (i) the release of alkaline metals and chloride is not significantly influenced by carbonation and (ii) the release of Ca and Pb is governed by chemical equilibria in pore water and diffusion, while their speciation in the leachate is determined by pH and the presence of carbonate ions.

Air Pollutants↗

The leaching behavior of cement stabilized air pollution control residues: a comparison of field and laboratory investigations.

The factors controlling leachate composition of cement stabilized air pollution control (APC) residues (41% APC residues, 22% cement, 3% Na2CO3, and 32% water, w/w) have been investigated both in the laboratory and in a pilot landfill. Batch leaching and tank leaching tests were carried out in the laboratory in order to determine solubility controlling phases and diffusion controlled species. The major species Ca, SO4, Al, and Si could be partially modeled by assuming calcium silicate hydrate (C-S-H), portlandite, and ettringite to be the solubility controlling phases both in field and laboratory. There were obviously additional minerals that could not be taken into account in calculations because of the lack of data. The determined effective diffusion coefficients (De) for Na and K (2.18e-12 and 5.43e-12 m2s-1) were used to model field concentrations. Agreement with field data was good. Heavy metal concentrations were in the range of 10(-8) mol dm-1 (Cd, Co, Cu, Mn, Ni) to 10(-6) mol dm-1 (Mo, Pb, W, Zn) in all experiments and often lower in the field leachate than expected from batch experiments. In laboratory experiments, the solubility of Mo and W was most probably controlled by their calcium metalates, Cu by CuO, Ni by Ni(OH)2, and Zn probably by a Zn containing C-S-H phase. In the field, diffusion seems to control Mo and W leachability, with calculated De values of 3.49e-14 and 1.35e-15 m2s-1.

Air Pollutants↗

Lead analysis by anti-chelate fluorescence polarization immunoassay.

Lead concentrations were determined by a fluorescence polarization immunoassay (FPIA) method that uses polyclonal antibodies raised against the lead(II) chelate of ethylenediamine-N,N,N',N'-tetraacetic acid (EDTA). The technique is based on competition for a fixed concentration of antibody binding sites between Pb-EDTA, formed by treating the sample with excess EDTA, and a fixed concentration of a fluorescent analogue of the Pb-EDTA complex. The objective was to correlate results obtained by FPIA with those produced by conventional atomic spectroscopy analysis of soils, solid waste leachates (produced by the Toxicity Characteristic Leachate Procedure; TCLP), airborne dust, and drinking water. Linear regression analysis of FPIA results for 138 soil samples containing 0-3094 ppm Pb(II) by flame atomic absorption spectroscopy and 40 TCLP extracts containing 0-668 ppm Pb(II) by inductively coupled plasma atomic emission spectroscopy produced correlation coefficients (r2) of 0.96 and 0.93, respectively. Pilot studies of mineral acid extracts of airborne dust trapped on fiberglass filters and of two sources of drinking water demonstrated the feasibility of also measuring lead in these matrixes by FPIA. The limit of detection under conditions that minimized sample dilution was approximately 1 ppb, and cross reactivity with 15 nontarget metals was below 0.5% in all cases. The methods are simple to perform and are amenable to field testing and mobile laboratory use, allowing timely and cost-effective characterization of suspected sources of lead contamination.

Air Pollutants↗

The use of box lysimeters with freshly contaminated soils to study the phytoremediation of recalcitrant organic contaminants.

The potential for phytoremediation of soil contaminated by trinitrotoluene (TNT) and 2,2',5,5'-tetrabromobiphenyl (PBB was used as a surrogate for PCBs) was examined in a 2-year study using box lysimeters under field conditions. The treatments were a warm season grass, Johnson grass, and a cool season grass, Canadian wildrye, and a rotation of Johnson grass and wildrye plus a fallow condition. The experiment was conducted using 12 large (1.50 m x 1.50 m x 0.75 m), in-ground, box lysimeters filled with a Weswood silt-loam soil freshly spiked with the TNT and PBB compounds to a concentration of 10 mg kg(-1) for each chemical. The lysimeters were sheltered to permit controlled applications of water. A total of five sampling rounds were conducted where soil, herbage, and leachate samples were collected for laboratory analysis. TNT and PBB concentrations were determined using the U.S. EPA approved immunoassay test procedures. In the soil, TNT concentrations dropped below the detection limit of 0.25 mg kg(-1) by day 92 and PBB concentrations dropped below the detection limit of 0.50 mg kg(-1) by day 184. There were no significant differences in chemical concentrations among any of the vegetated or fallow treatments at a significance level of alpha < 0.05. However, PBB soil concentrations rebounded above the 0.50 mg kg(-1) level by day 720 for all treatments. No detectable concentrations of TNT or PBB were found in any of the herbage samples or in the leachate.

Biodegradation, Environmental↗

Dissipation of fragrance materials in sludge-amended soils.

A possible removal mechanism for fragrance materials (FMs) in wastewater is adsorption to sludge, and sludge application to land may be a route through which FMs are released to the soil environment. However, little is known about the concentrations and fate of FMs in soil receiving sludge application. This study was conducted to better understand the dissipation of FMs in sludge-amended soils. We first determined the spiking and extraction efficiencies for 22 FMs in soil and leachate samples. Nine FMs were detected in digested sludges from two wastewater treatment plants in Delaware using these methods. We conducted a 1-year die-away experiment which involved four different soils amended with sludge, with and without spiking of the 22 FMs. The initial dissipation of FMs in all spiked trays was rapid, and only seven FMs remained at concentrations above the quantification limits after 3 months: AHTN, HHCB, musk ketone, musk xylene, acetyl cedrene, OTNE, and DPMI. After 1 year, the only FMs remaining in all spiked trays were musk ketone and AHTN. DPMI was the only FM that leached significantly from the spiked trays, and no FMs were detected in leachate from any unspiked tray. While soil organic matter content affected the dissipation rate in general, different mechanisms (volatilization, transformation, leaching) appeared to be important for different FMs.

Adsorption↗

Contribution of natural organic matter to copper leaching from municipal solid waste incinerator bottom ash.

The leaching of heavy metals, such as copper, from municipal solid waste incinerator (MSWI) bottom ash is a concern in many countries and may inhibit the beneficial reuse of this secondary material. The enhanced leaching of copper from three MSWI bottom ash samples by dissolved organic carbon (DOC) was investigated with specific attention for the nature of the organic ligands. A competitive ligand exchange-solvent extraction (CLE-SE) method was used to measure Cu binding to DOC. Two types of binding sites for Cu were identified and geochemical modeling showed that the organically bound fraction varied from 82% to 100% between pH 6.6 and 10.6. Model calculations showed that complexation by previously identified aliphatic and aromatic acids was unable to explain the enhanced Cu leaching from the MSWI residues. High-performance size-exclusion chromatography (HPSEC) and the standard extraction procedure to isolate and purify natural organic matter revealed that about 0.5% of DOC consists of humic acids and 14.3-25.6% consists of fulvic acids. Calculated Cu binding isotherms based on these natural organic compounds, and the nonideal competitive adsorption-Donnan (NICA-Donnan) model, provide an adequate description of the organic Cu complexation in the bottom ash leachates. The results show that fulvic acid-type components exist in MSWI bottom ash leachates and are likely responsible for the generally observed enhanced Cu leaching from these residues. These findings enable the use of geochemical speciation programs, which include models and intrinsic parameters for metal binding to natural organic matter, to predict Cu leaching from this widely produced waste material under variable environmental conditions (e.g., pH, ionic strength, and concentrations of competing metals). The identified role of fulvic acids in the leaching of Cu and possibly other heavy metals can also be used in the development of techniques to improve the environmental quality of MSWI bottom ash.

Air Pollutants↗